C41H59NO5 (645.91): C 76.24, H 9.21, N 2.17; found: 76.10, H 9.37, N 2.09.
4.1.5.3. Ethyl (3β) 3-([Boc-D-tryptophanyl]oxy)-11-oxo-olean-12-en-30-oate (15)
Compound 15 was obtained from GA-Et (466 mg, 0.94 mmol) by method A as a colorless powder, using boc-D-
tryptophane (230 mg, 1.13 mmol) and DCC (233 mg, 1.13 mmol); m.p. 106-110 °C; RF = 0.49 (hexane/ethyl acetate,
7:3); [α]D = 98.62° (c 0.52, CHCl3); UV-Vis (MeOH): λmax (log ε) = 241 nm (4.62), 269 nm (4.22); IR (KBr): ν = 3386
(br), 2976 (s), 1726 (s), 1659 (s), 1498 (m), 1458 (m), 1390 (m), 1366 (m), 1251 (m), 1216 (s), 1173 (s), 1086 (m), 1049
1
(m), 1020 (m), 987 (m), 740 (m) cm-1; H NMR (500 MHz, CDCl3): δ = 8.09 (br, 1H, Trp-NH), 7.60 (d, 1H, indole-7, J
= 7.8 Hz), 7.33 (d, 1H, indole-4, J = 8.1 Hz), 7.17 (dd, 1H, indole-5, J = 8.1, 7.8 Hz), 7.10 (dd, 1H, indole-6, J = 7.6,
7.6 Hz), 7.00 (s, 1H, indole-2), 5.63 (s, 1H, H-12), 5.08 (d, 1H, Trp-CHNH, J = 7.7 Hz), 4.65 (m, 1H, Trp-CHNH), 4.45
(dd, 1H, H-3, J = 9.8, 6.7 Hz), 4.18 (dq, 1H, Et-CHH′, J = 10.7, 7.2 Hz), 4.12 (dq, 1H, Et-CHH′, J = 10.7, 7.2 Hz), 3.27
(m, 2H, Trp-CH2), 2.75 (ddd, 1H, H-1, J = 13.4, 3.4, 3.4 Hz), 2.33 (s, 1H, H-9), 2.10 (dd, 1H, H-18, J = 12.9, 3.6 Hz),
2.02 (m, 1H, H-15), 1.99 (m, 1H, H-21), 1.92 (ddd, 1H, H-19, J = 13.6, 3.8, 2.5 Hz), 1.81 (ddd, 1H, H-16, J = 13.7,
13.7, 4.6 Hz), 1.64 (m, 1H, H-7), 1.60 (dd, 1H, H-19′, J = 13.5, 13.5 Hz), 1.52 (m, 1H, H-6), 1.50 (m, 1H, H-2), 1.43 (s,
12H, Boc-CH3 and H-28), 1.41 (m, 1H, H-6′), 1.38 (m, 1H, H-7′), 1.36 (m, 1H, H-22), 1.35 (s, 3H, H-27), 1.34 (m, 1H,
H- 22′), 1.30 (m, 1H, H-21′), 1.26 (t, 3H, Et-CH3, J = 7.2), 1.17 (m, 1H, H-16′), 1.14 (s, 3H, H-23), 1.11 (s, 6H, H-25
and H-26), 1.00 (m, 1H, H-15′), 0.98 (m, 1H, H-1′), 0.80 (s, 3H, H-29), 0.79 (m, 1H, H-5), 0.77 (s, 3H, H-24) ppm; 13C
NMR (125 MHz, CDCl3): δ = 200.1 (C-11), 176.4 (C-30), 172.1 (Trp-COO), 169.5 (C-13), 153.1 (Boc-COO), 136.1
(indole-q.C), 128.4 (C-12), 128.3 (indole-q.C), 122.6 (indole-2), 122.1 (indole-5), 119.5 (indole-6), 119.1 (indole-7),
111.0 (indole-4), 110.5 (indole-q.C), 81.9 (C-3), 79.6 (Boc-q.C), 61.6 (C-9), 60.4 (Et-CH2), 55.0 (C-5), 54.3 (Trp-
CHNH), 48.4 (C-18), 45.4 (C-14), 43.8 (C-20), 43.2 (C-8), 41.0 (C-19), 38.6 (C-1), 38.0 (C-10), 37.7 (C-22), 36.8 (C-
4), 32.6 (C-7), 31.8 (C-17), 31.1 (C-21), 28.5 (C-29), 28.3 (C-28), 28.3 (C-23), 27.9 (Trp-CH2), 26.4 (C-16), 26.4 (C-
15), 23.3 (C-27), 23.2 (C-2), 18.6 (C-26), 17.3 (C-6), 16.5 (C-24), 16.3 (C-25), 14.3 (Et-CH3) ppm; MS (ESI, MeOH):
m/z = 785.3 ([M+H]+, 23), 807.3 ([M+Na]+, 100); analysis calculated for C48H68N2O7 (785.06): C 73.44, H 8.73, N
3.57; found: 72.29, H 8.91, N 3.42.
4.1.5.4. Ethyl (3β) 3-([D-tryptophanyl]oxy)-11-oxo-olean-12-en-30-oate (16)
Compound 16 was obtained from compound 15 (127 mg, 0.16 mmol) by method B as a colorless powder; yield: 105
mg, 96 %. m.p. 91-95 °C; RF = 0.37 (DCM/MeOH, 9:1); [α]D = 96.48° (c 0.61, CHCl3); UV-Vis (MeOH): λmax (log ε) =
226 nm (4.62), 240 nm (4.61), 266 nm (4.18); IR (KBr): ν = 3407 (br), 2950 (s), 1727 (s), 1658 (s), 1458 (m), 1388 (m),
1280 (w), 1215 (s), 1176 (m), 1087 (m), 1020 (w) cm-1; 1H NMR (500 MHz, CDCl3): δ = 8.21 (s, 1H, Trp-NH), 7.61 (d,
1H, indole-7, J = 7.7 Hz), 7.35 (d, 1H, indole-4, J = 7.9 Hz), 7.18 (m, 1H, indole-5), 7.12 (m, 1H, indole-6), 7.09 (s, 1H,
indole-2), 5.64 (s, 1H, H-12), 4.50 (dd, 1H, H-3, J = 11.4, 5.0 Hz), 4.18 (dq, 1H, Et-CHH′, J = 10.9, 7.1 Hz), 4.12 (dq,
1H, Et-CHH′, J = 10.9, 7.1 Hz), 3.89 (m, 1H, Trp-CHNH2), 3.31 (dd, 1H, Trp-CHH′, J = 14.9, 4.6 Hz), 3.09 (dd, 1H,
Trp-CHH′, J = 14.8, 7.8 Hz), 2.78 (ddd, 1H, H-1, J = 13.6, 3.7, 3.7 Hz), 2.42 (br, 2H, NH2), 2.34 (s, 1H, H-9), 2.10 (dd,
1H, H-18, J = 13.6, 3.8 Hz), 2.03 (m, 1H, H-15), 1.99 (m, 1H, H-21), 1.92 (ddd, 1H, H-19, J = 13.4, 3.9, 2.7 Hz), 1.82
(ddd, 1H, H-16, J = 13.7, 13.7, 4.2 Hz), 1.65 (m, 1H, H-7), 1.63 (m,1H, H-2), 1.61 (dd, 1H, H-19′, J = 13.6, 13.6 Hz),
1.59 (m, 1H, H-2′), 1.56 (m, 1H, H-6), 1.43 (m, 1H, H-6′), 1.40 (m, 1H, H-7′), 1.38 (m, 1H, H-22), 1.36 (s, 3H, H-27),
1.34 (m, 1H, H-22′), 1.31 (m, 1H, H-21′), 1.26 (t, 3H, Et-CH3, J = 7.1 Hz), 1.17 (m, 1H, H-16′), 1.14 (s, 3H, H-28), 1.13
(s, 3H, H-25), 1.11 (s, 3H, H-26), 1.02 (m, 1H, H-15′), 1.00 (m, 1H, H-1′), 0.83 (s, 3H, H-24), 0.82 (s, 3H, H-23), 0.80
(s, 3H, H-29), 0.79 (m, 1H, H-5) ppm; 13C NMR (125 MHz, CDCl3): δ = 200.0 (C-11), 176.4 (C-30), 169.4 (C-13),
10